CN101275242A - Electrolyte additive for producing copper starting sheet and use method thereof - Google Patents
Electrolyte additive for producing copper starting sheet and use method thereof Download PDFInfo
- Publication number
- CN101275242A CN101275242A CNA2007103036359A CN200710303635A CN101275242A CN 101275242 A CN101275242 A CN 101275242A CN A2007103036359 A CNA2007103036359 A CN A2007103036359A CN 200710303635 A CN200710303635 A CN 200710303635A CN 101275242 A CN101275242 A CN 101275242A
- Authority
- CN
- China
- Prior art keywords
- gelatin
- dete
- starting sheet
- hydrochloric acid
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to an electrolyte additive used for producing copper initiated plate electrode and the use method, which is characterized in that the invention is formed by mixing Andert, gelatin, thiourea, hydrochloric acid in proportion, the mass ratio is andert: gelatin: thiourea: hydrochloric acid = 1:(3.27 to 4.31):(1.23 to 1.72):(0.13 to 0.19). The invention is characterized in that the produced initiated plate electrode has less chemical composition of impurities, smooth physical surface smooth, dense crystal and uniform thickness. The initiated plate electrode has better overhanging degrees after being processed by joint unit. The invention is an initiated plate electrode production technology which can stably improved the quality of high-purity copper cathode.
Description
Technical field
The present invention relates to a kind of electrolysis additive and using method of production of copper starting sheet
Technical background
In electrolytic refining course of copper,, in electrolytic solution, add surfactant-additive in order to obtain the poor high-quality cathode copper of compact structure, smooth surface, gas and other detrimental impurity.The main component of additive commonly used has gelatin, thiocarbamide and hydrochloric acid at present.Because gelatin is a hmw protein, bad dissolving adopted normal-temperature water to soak usually and dissolved in 12～24 hours.Because this method soak time is long, has following defective: (1) is easily contaminated rotten; (2) when soaking, the container of use is many, and occupation space is big; Need when (3) dissolving soaked gelatin in the prethawing container is moved in the additive steel basin, be prone to the operation deviation, cause metering inaccurate, and labour intensity is big; (4) because pre-ization volume is big, and temperature is low, is difficult to be implemented in molten some temperature controlling under a certain amount of dilution volume, it is undesirable usually to dissolve effect; (5) because volume restrictions is mixed inhomogeneous; (6) need clean a large amount of containers every day, the careless slightly solution that just causes is rotten, then quality product is impacted.
In the cathode copper production process,, under peracid, high current density electrolysis manufacturing condition, adopt the starting sheet of above-mentioned gelatin, thiocarbamide and hydrochloric acid Additive Production to have following defective because positive plate impurity component content is higher:
(1) content of impurities of starting sheet is higher, and the starting sheet content of impurities of production is 66.7ppm, is higher than the foreign matter content of Cu-CATH-1.When Cu-CATH-1 is produced, use content of impurities rising 2～3ppm that this starting sheet makes Cu-CATH-1.
(2) machining property is relatively poor, and the quality of starting sheet is more crisp hard, and surface crystallization is coarse, and thin and thick is irregular.Therefore, the defective of starting sheet is come out through the obvious expression in interlock unit processing back, thereby necessary 100% flat board behind last groove, defective behind the flat board and problem display again when electrolysis, need to strengthen looking into groove, and the negative impact that causes when looking into groove can be following, not only the labor strength height, and it is general to make counter productive be snowball, finally has influence on a plurality of productive capacitys.
(3) quality of separating out of cathode copper is stablized inadequately, and crystallization is not fine and close;
(4) flocculating effect of the floating anode sludge is bad in the electrolytic solution, very easily sticks to cathode surface and forms the knot grain.
Summary of the invention
The objective of the invention is the defective that exists at above-mentioned prior art, provide a kind of simple to operate, solute effect good, help stable and improve the electrolysis additive and the using method of the production of copper starting sheet of Cu-CATH-1 quality.
The objective of the invention is to be achieved through the following technical solutions.
A kind of electrolysis additive of production of copper starting sheet, it is characterized in that this additive is made up of the An Dete that is mixed in proportion, gelatin, thiocarbamide, hydrochloric acid, its quality proportioning consists of An Dete: gelatin: thiocarbamide: HCl=1: (3.27～4.31): (1.23～1.72): (0.13～0.19).
The using method of the electrolysis additive of a kind of production of copper starting sheet of the present invention is characterized in that the step of its use comprises:
(1) will be by the load weighted An Dete of quality proportioning, gelatin, thiocarbamide uniform mixing, water melts under 65～70 ℃ of temperature, is diluted to concentration 5～20g/L, stirs 60-90 minute;
(2) take by weighing hydrochloric acid in proportion, be diluted to 20～40g/L;
(3) will prepare An Dete, gelatin, thiourea additives mixed solution and hydrochloric acid soln and add in the circular electrolyte continuously respectively, and wherein add An Dete, gelatin, thiourea additives mixed solution and electrolytic solution ratio and be: 1: (200～300); The hydrochloric acid soln that adds and the ratio of electrolytic solution are: 1: (200～300).
The using method of the electrolysis additive of a kind of production of copper starting sheet of the present invention, the An Dete after it is characterized in that preparing, gelatin, thiocarbamide uniform mixing additive solution will use in 24 hours.
In the method for the invention, the key factor of decision additive preparation effect has 2 points: the one, and water temperature, the height of water temperature can influence the performance of additive effect; The 2nd, stir, churning time has determined whether additive dissolves fully, whether mix even, more than 2 quality that all can influence starting sheet.
After An Dete and gelatin are used, increased the action intensity of gelatin, in certain hour, certain temperature range, An Dete can make the action intensity of gelatin tend towards stability; In addition, the add-on of An Dete does not influence the action intensity of thiocarbamide and hydrochloric acid anticathode copper, thereby makes the additive controlled levels improve a level.
Owing to taked above-mentioned technical approach, the present invention is compared with original technology: the starting sheet quality of output is good, smooth densification, and thin and thick is even, and the impurity summation is reduced to below the 40ppm by 66.7ppm.The pliable and tough appropriateness of starting sheet of producing, thin and thick is even, foreign matter content is low, can satisfy the processing request of interlock unit, and the precision height that dangles of the starting sheet after the processing, and its technological operation is simple, production effect good.
Embodiment
A kind of electrolysis additive of production of copper starting sheet, this additive is made up of the An Dete that is mixed in proportion, gelatin, thiocarbamide, hydrochloric acid, and its quality proportioning consists of An Dete: gelatin: thiocarbamide: HCl=1: (3.27～4.31): (1.23～1.72): (0.13～0.19).
The step of use comprises:
(1) will be by the load weighted An Dete of quality proportioning, gelatin, thiocarbamide uniform mixing, water melts under 65～70 ℃ of temperature, is diluted to concentration 5～20g/L, stirs 60-90 minute;
(2) take by weighing hydrochloric acid in proportion, be diluted to 20～40g/L;
(3) will prepare An Dete, gelatin, thiourea additives mixed solution and hydrochloric acid soln and add in the circular electrolyte continuously respectively, and wherein add An Dete, gelatin, thiourea additives mixed solution and electrolytic solution ratio and be: 1: (200～300); The hydrochloric acid soln that adds and the ratio of electrolytic solution are: 1: (200～300).
The electrolysis additive of a kind of production of copper starting sheet of the present invention, it is as follows to be used for the electrolytic copper technology condition: Cu
2+: 48～55g/L, H
2SO
4: 170～190g/L, Ni
2+:＜15g/L, temperature: 60～65 ℃, internal circulating load: 25～30L/min, current density: 280A/m
2, cathode deposition period: 21h, plant sheet material matter: titanium, plant plate gauge lattice: 1120 * 1010 * 3mm.
The positive plate chemical ingredients sees Table 1
Table 1 positive plate chemical ingredients (%)
A) adopt the new additive agent proportioning to produce starting sheet test technology technical qualification
Copper anode plate: outsourcing material copper anode plate specification is 1000 * 960 * 42mm, and weight is the 320kg/ sheet.
Embodiment 1
Additive: An Dete, gelatin, thiocarbamide, hydrochloric acid (mass ratio): An Dete: gelatin: thiocarbamide: HCl=1: 3.57: 1.43: 0.16
Embodiment 2
Additive: An Dete, gelatin, thiocarbamide, hydrochloric acid (mass ratio): An Dete: gelatin: thiocarbamide: HCl=1: 4: 1.5: 0.15
The preparation of additive: take by weighing the additive capacity that need add the same day with weigher, with the hot water dissolving of certain temperature, stir up to dissolving fully, put into the additive scale tank, moisturizing is to prescribed volume, 24 hours even adding systems.Gelatin, thiocarbamide, An Dete mixed preparing, hydrochloric acid is prepared separately.
Embodiment 1 at first adds substrate in electrolytic solution: gelatin 1071g, thiocarbamide 429g, An Dete 300g, HCl 48g.
Embodiment 2 at first adds substrate in electrolytic solution: gelatin 1400g, thiocarbamide 525g, An Dete 350g, HCl 52.5g.
B) test control other technology condition (seeing Table 2)
Table 2 starting sheet production test data
2 test-results
Randomly draw part test and produce starting sheet and original pole piece, every starting sheet is got at 8 and is detected its thickness, sees Table 3, table 4.From detecting data contrast situation, the starting sheet uniformity coefficient of test output significantly improves, and the starting sheet chemical ingredients (01～05 batch) of test output sees Table 5.
The original pole piece thickness of table 3 (conduction time 22.3h, current density 280A/m
2)
Starting sheet thickness (conduction time 21.065h, current density 280A/m are produced in table 4 test
2)
Last table explanation, the thickness difference of novel process starting sheet is reduced to 0.24mm by 0.36mm, and uniformity coefficient significantly improves.
Table 5 starting sheet chemical ingredients (ppm)
The test the starting sheet that produces compare with original pole piece, foreign matter content is reduced to below the 38.1ppm by 66.7ppm before, all reaches national Cu-CATH-1 standard.
The novel process starting sheet is because the good variation of performance, make the starting sheet degree of dangling after the processing of interlock unit improve, reduced sticking, adhering to of the various anode sludge after going into groove, the defective of electrolytic process obviously reduces simultaneously, the foreign matter content of cathode copper reduces (seeing Table 6), and the physical appearance quality is good.
Table 6 cathode copper chemical ingredients cartogram (ppm)
Claims (3)
1. the electrolysis additive of a production of copper starting sheet, it is characterized in that this additive is made up of the An Dete that is mixed in proportion, gelatin, thiocarbamide, hydrochloric acid, its quality proportioning consists of An Dete: gelatin: thiocarbamide: HCl=1: (3.27～4.31): (1.23～1.72): (0.13～0.19).
2. the using method of the electrolysis additive of a kind of production of copper starting sheet according to claim 1 is characterized in that the step of its use comprises:
(1) will be by the load weighted An Dete of quality proportioning, gelatin, thiocarbamide uniform mixing, water melts under 65～70 ℃ of temperature, is diluted to concentration 5～20g/L, stirs 60-90 minute;
(2) take by weighing hydrochloric acid in proportion, be diluted to 20～40g/L;
(3) will prepare An Dete, gelatin, thiourea additives mixed solution and hydrochloric acid soln and add in the circular electrolyte continuously respectively, and wherein add An Dete, gelatin, thiourea additives mixed solution and electrolytic solution ratio and be: 1: (200～300); The hydrochloric acid soln that adds and the ratio of electrolytic solution are: 1: (200～300).
3. the using method of the electrolysis additive of a kind of production of copper starting sheet according to claim 1, the An Dete after it is characterized in that preparing, gelatin, thiocarbamide uniform mixing additive solution will use in 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103036359A CN101275242A (en) | 2007-12-20 | 2007-12-20 | Electrolyte additive for producing copper starting sheet and use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103036359A CN101275242A (en) | 2007-12-20 | 2007-12-20 | Electrolyte additive for producing copper starting sheet and use method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101275242A true CN101275242A (en) | 2008-10-01 |
Family
ID=39995085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007103036359A Pending CN101275242A (en) | 2007-12-20 | 2007-12-20 | Electrolyte additive for producing copper starting sheet and use method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101275242A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102009169A (en) * | 2009-09-07 | 2011-04-13 | 福田金属箔粉工业株式会社 | Electrolytic copper powder and manufacturing method thereof |
| CN103726070A (en) * | 2013-12-13 | 2014-04-16 | 金川集团股份有限公司 | Copper electrolyte additive and application method thereof |
| CN113564639A (en) * | 2021-07-27 | 2021-10-29 | 金川集团股份有限公司 | Process for producing cathode copper by electrolytic refining of low-grade copper anode plate |
-
2007
- 2007-12-20 CN CNA2007103036359A patent/CN101275242A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102009169A (en) * | 2009-09-07 | 2011-04-13 | 福田金属箔粉工业株式会社 | Electrolytic copper powder and manufacturing method thereof |
| CN103726070A (en) * | 2013-12-13 | 2014-04-16 | 金川集团股份有限公司 | Copper electrolyte additive and application method thereof |
| CN113564639A (en) * | 2021-07-27 | 2021-10-29 | 金川集团股份有限公司 | Process for producing cathode copper by electrolytic refining of low-grade copper anode plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102713022B (en) | Cathode copper plating phosphorous copper anode, its manufacture method and plating method of electrocytic copper | |
| KR20130140568A (en) | High-purity electrolytic copper and electrolytic refining method thereof | |
| CN101275242A (en) | Electrolyte additive for producing copper starting sheet and use method thereof | |
| KR101535853B1 (en) | Manufacturing method of high strength copper foil using micro-hardening and high strength copper foil manufactured by the same | |
| CN101914801A (en) | Anodic phosphorous copper balls and preparation method thereof | |
| CN112981474A (en) | High-strength copper foil and preparation method thereof | |
| CN105002524A (en) | Addition agent and process for producing 6-micron low-warping-degree electrolytic copper foil through addition agent | |
| CN117646259B (en) | Method for preparing gold-silver alloy coating, corresponding coating and product | |
| JP6365395B2 (en) | Method for producing nickel sulfate | |
| CN102844472A (en) | High-purity copper anode for copper electroplating, method for producing same, and copper electroplating method | |
| US3793161A (en) | Methods for electroplating solder | |
| CN108823610A (en) | Additive for electrolytic copper foil and 5 microns of double light lithium electricity electrolytic copper foil production technologies | |
| CN104846407A (en) | Additive and process for producing 6mu.m high-tensile-strength electrolytic copper foil by using same | |
| CN103726070A (en) | Copper electrolyte additive and application method thereof | |
| CN104726904A (en) | Auxiliary additive for potassium chloride or sodium chloride galvanizing process | |
| CN109851216B (en) | Composite clarifying agent for producing ultra-white glass by float process | |
| US6309529B1 (en) | Method for producing sputtering target material | |
| CN112281187A (en) | Composite additive for preparing electrolytic nickel and preparation method thereof | |
| CN101604742A (en) | A kind of graphite water-base cathode formula and preparation method | |
| TWI838979B (en) | Brittle Electrodeposited Copper | |
| CN104862737A (en) | Copper electrolyte addition agent loaded with nanocarbon and preparation method of addition agent | |
| CN111206272B (en) | Plating solution additive and plating solution for electroplating matte tin on heterojunction cell, and preparation method and application of plating solution additive and plating solution | |
| KR101860468B1 (en) | Ionic liquid electrolyte composition for electroless plating | |
| CN118773686A (en) | Additive for improving hardness of gold cyanide-free electroforming process product and application thereof | |
| JP2000054181A (en) | Method for electrolytically refining copper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081001 |